Process of preparing diaminopyridine compounds

ABSTRACT

A process for preparing diaminopyridines of the formula ##STR1## where one of the two radicals X 1  and X 2  is hydrogen, C 1  -C 4  -alkyl, halogen or nitro and the other is cyano, 
     R 1  is hydrogen, C 1  -C 4  -alkyl or phenyl, 
     R 2  and R 3  are each hydrogen, C 1  -C 4  -alkyl or C 1  -C 4  -alkoxy, 
     R 4  is hydrogen or C 1  -C 4  -alkyl, and 
     R 5  is optionally substituted C 1  -C 10  -alkyl, C 3  -C 4  -alkenyl or C 5  -C 7  -cycloalkyl, 
     by reacting dichloropyridines of the formula ##STR2## in a first step with an amine of the formula R 5  -NH 2  at from 10° to 80° C. in the presence of a base and of an inert organic diluent and/or water, then removing the diluent and thereafter, with or without prior intermediate isolation of the reaction product, comprises carrying out the second step in a melt at from 90° to 165° C. and at a pH from 3.5 to 6.5 using from 1.3 to 3 mol of aniline IV are used per mole of dichloropyridine II.

This application is a 371 of PCT/EP93/00538, filed Mar. 10, 1993.

The present invention relates to a novel process for preparing 2,6-diaminocyanopyridines by reacting the 2,6-dichloro compounds with amines.

U.S. Pat. No. 3,853,895 discloses the preparation of 2,6-diaminopyridines. However, the manner of preparation described therein is unsatisfactory, since large amounts of amine are required and, what is more, the target products are obtained only in a low yield.

Furthermore, DE-A-2 260 827, DE-A-2 916 319 and U.S. application Ser. No. 3,980,659 describe the preparation of 2,6-diaminocyanopyridines using the corresponding dichloro or aminomonochloro compounds as starting materials.

It is an object of the present invention to provide a novel process for preparing 2,6-diaminocyanopyridines which likewise starts from the 2,6-dichloro compounds and gives the target products in a simple manner and in high yield and purity.

We have found that this object is achieved in an advantageous manner by a process for preparing diaminopyridines of the formula I ##STR3## where

one of the two radicals X¹ and X² is hydrogen, C₁ -C₄ -alkyl, halogen or nitro and the other is cyano,

R¹ is hydrogen, C₁ -C₄ -alkyl or phenyl,

R² and R³ are each independently of one another hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy,

R⁴ is hydrogen or C₁ -C₄ -alkyl, and

R⁵ is C₁ -C₁₀ -alkyl which may be interrupted by from 1 to 3 oxygen atoms in ether function and is optionally hydroxyl-, C₁ -C₄ -alkanoyloxy-, phenoxy-, phenyl-, tetrahydrofuranyl- or tetrahydropyranyl-substituted, C₃ -C₄ -alkenyl or C₅ -C₇ -cycloalkyl,

by reacting dichloropyridines of the formula II ##STR4## where R¹ and X¹ are each as defined above, with amines by reacting in a first step a dichloropyridine of the formula II with an amine of the formula III

    R.sup.5 --NH.sub.2                                         (III)

where R⁵ is as defined above, at from 10° to 80° C. in the presence of a base and of an inert organic diluent and/or water, then removing the diluent and thereafter, with or without prior intermediate isolation of the reaction product, reacting it in a second step with an aniline of the formula IV ##STR5## where R², R³ and R⁴ are each as defined above, which comprises carrying out the second step in a melt at from 90° to 165° C. and at a pH from 3.5 to 6.5 using 1.3 to 3 mol of aniline IV per mole of dichloropyridine II.

Any alkyl appearing in the abovementioned formulae may be not only straight-chain but also branched.

R¹, R², R³, R⁴, R⁵, X¹ and X² are each for example methyl, ethyl, propyl, isopropyl, butyl, isobutyl or sec-butyl.

R⁴ may also be for example methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy or sec-butoxy.

R⁵ may also be for example pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl, benzyl, 1- or 2-phenylethyl, 2- or 3-phenylpropyl, 3-phenylprop-2-yl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 3- hydroxyprop-2-yl, 2-hydroxybutyl, 4-hydroxybutyl, 5-hydroxypentyl, 6-hydroxyhexyl, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl, 2-butoxyethyl, 2- or 3-methoxypropyl, 2- or 3-ethoxypropyl, 2- or 3-propoxypropyl, 2- or 3-butoxypropyl, 2- or 4-methoxybutyl, 2- or 4-ethoxybutyl, 2- or 4-propoxybutyl, 2- or 4-butoxybutyl, 3,6-dioxaheptyl, 3,6-dioxaoctyl, 4,8-dioxanonly, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl, 4,7-dioxanonyl, 4,8-dioxadecyl, 3,6,9-trioxadecyl, 3,6,9-trioxaundecyl, 4,8,12-trioxatridecyl, 2-phenoxyethyl, 2-phenoxypropyl, 3-phenoxypropyl, 2-phenoxybutyl, 4-phenoxybutyl, 5-phenoxypentyl, 6-phenoxyhexyl, 5-hydroxy-3-oxapentyl, 8-hydroxy-4-oxaoctyl, 6 -phenoxy-4-oxahexyl, 2-formyloxyethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2- or 3-formyloxypropyl, 2- or 3-acetyloxypropyl, 2- or 3-propionyloxypropyl, 2- or 4-formyloxybutyl, 2- or 4-acetyloxybutyl, 2- or 4-propionyloxybutyl, 2-(tetrahydropyran-4-yl)ethyl, 2- or 3-(tetrahydropyran-4-yl)-propyl, 2- or 4-(tetrahydropyran-4-yl)butyl, prop-2-en-1-yl, but-2-en-1-yl, 2-methylprop-2-en-1-yl, cyclo-pentyl, cyclohexyl or cycloheptyl.

X¹ and X² may each also be example fluorine, chlorine and bromine.

Preference is given to a process for preparing diaminopyridines of the formula I where X¹ is hydrogen and X² is cyano.

Further preference is given to a process for preparing diaminopyridines of the formula I where R¹ is methyl.

Further preference is given to a process for preparing diaminopyridines of the formula I where R², R³ and R⁴ are each hydrogen.

Further preference is given to a process for preparing diaminopyridines of the formula I where R² is methyl or methoxy and R³ and R⁴ are each hydrogen or methyl or where R² and R³ are each methyl and R⁴ is hydrogen.

Further preference is given to a process for preparing diaminopyridines of the formula I where R⁵ is C₁ -C₈ -alkyl which may be interrupted by 1 or 2 oxygen atoms in ether function and is optionally hydroxyl- or phenyl-substituted, or allyl.

In the process of the invention, the first step (step 1) is carried out in the presence of an inert organic diluent and/or water. Suitable diluents are in particular those which are either completely immiscible with water or which are miscible with water only to a limited extent. Examples are isobutanol, toluene, o-, m- or p-xylene, ethylbenzene and mixtures thereof. The use of isobutanol, toluene or xylene is preferred.

Suitable bases for use in the first step are for example alkali metal carbonates or bicarbonates, such as sodium or potassium carbonate or bicarbonate. The use of sodium carbonate is preferred.

The second step (step 2) of the novel process is carried out at a pH from 3.5 to 6.5, preferably from 4 to 5.5. Since it is difficult to determine the pH in a melt, it is advisable, every time the pH of the melt is to be determined, to add a sample of the melt to water and to determine the pH of the aqueous system. The above-mentioned pH can be set not only with organic but also with inorganic acids. Suitable acids are for example sulfuric acid, hydrochloric acid and p-toluenesulfonic acid. The use of p-toluenesulfonic acid is preferred.

In the process of the invention the molar ratio of dichloropyridine II:amine III is from 1:1.03 to 1:1.5, preferably from 1:1.05 to 1:1.25, and the molar ratio of dichloropyridine II:aniline IV is from 1:1.3 to 1:3, preferably from 1:1.5 to 1:3.

Per mole of dichloropyridine II it is customary to use in the first step from 1 to 2 mole equivalents, preferably from 1 to 1.3 mole equivalents, of a base.

Based on the weight of dichloropyridine II the amount of inert organic diluent used in the first step is in general from 10 to 150% by weight, preferably from 30 to 100% by weight.

To initiate the second-stage reaction it is in general sufficient to employ catalytic amounts of an acid.

The process of the invention is conveniently carried out by starting in the first step with an initial charge of dichloropyridine II and inert organic diluent and raising the temperature with stirring initially to 10°-80° C., preferably 45°-70° C., in particular 45°-60° C. To this mixture is added at the stated temperature the amine III and then the base. Thereafter the reaction is carried out at the stated temperature. When the reaction has ended, which in general takes from 12 to 24 hours, the reaction mixture can be acidified, diluted with water and then freed of the diluent-water mixture. This can be done for example by distillation. The diluent thus recovered can be recycled into the process.

In the first step the diaminopyridines of the formula I are obtained as isomer mixtures consisting predominantly of a product of the formula I where X¹ is hydrogen and X² is cyano and to a minor proportion of a product of the formula I where X¹ is cyano and X² is hydrogen when the reaction is carried out at up to 55° C. for about 12 hours.

The predominant diaminopyridine I (X¹ =H, X² =CN) is preferably isolated in a practically isomer-free state before the diluent is separated off and the second step is started. This can be done for instance by filtering off since, for example if toluene is used as diluent, the product in question is in general in the form of a precipitate.

To prepare those diaminopyridines of the formula I where R⁵ is an alkyl radical with a hydroxyl group, it is advisable in some cases to start not from the corresponding hydroxyalkylamines III but from their esterified compounds (C₁ -C₄ -alkanoyloxyalkyl compounds). Afterwards the alkanoyl group can be re-eliminated by hydrolysis.

By adding acid and aniline IV to the melt resulting from the removal of the diluent it is then possible to form the diaminopyridines I in the second step. The second reaction step is in general carried out at from 90° to 165° C., preferably at from 125° to 140° C. After the reaction has ended, which in general takes from 8 to 20 hours, the product is worked up.

This can be done in a conventional manner. For example, the reaction mixture can be diluted with water and isobutanol and be neutralized with a base, for example sodium hydroxide solution. Thereafter the water, the isobutanol and the excess aniline IV are distilled off under atmospheric pressure. The remaining aniline IV can be removed from the reaction mixture by distillation under reduced pressure. It is possible to recycle the aniline IV back into the reaction.

The resulting diaminopyridine of the formula I can either be further used in that form or be subjected to a reprecipitation. For this it is dissolved in concentrated hydrochloric acid and then reprecipitated with sodium hydroxide solution.

The process of the invention gives the diaminopyridines of the formula I in a simple manner and in high purity, in particular high isomer purity, and yield.

The diaminopyridines of the formula I are useful intermediates, in particular coupling components (X¹ /X² =H, CN), for the synthesis of dyes.

The Examples which follow illustrate the invention.

EXAMPLE 1

900 ml of isobutanol were mixed at room temperature with a mixture of 935 g of 2,6-diaminopyridine and 180 ml of water. Then the temperature is raised to 40° C. and a total of 479 g of 3-methoxypropylamine were added in the course of 1 hour with slight cooling. This was followed by stirring at from 40° to 45° C. for 2 hours, at which point 300 g of sodium carbonate were added. The mixture was stirred at from 40° to 45° C. for a further 2 hours and then the temperature was gradually raised to a maximum of 80° C. until the reaction has ended. The inorganic salts were then dissolved by adding 1000 ml of water, the mixture was acidified with sulfuric acid to pH 1, and the lower, aqueous layer, which contained the excess of amine, was separated off. The organic phase was then adjusted to pH 4-5 and then the isobutanol was removed by distillation. At 125° C. 1400 g of o-anisidine and 20 g of p-toluenesulfonic acid were added, and stirring was then continued at from 130° to 135° C. During the reaction the pH of a sample stirred into water/ methanol was monitored. The pH of the reaction mixture was maintained within the range from 4.5 to 5.5 by the regular addition of anhydrous sodium carbonate to the reaction mixture. A total of 216 g of sodium carbonate were required. Then the reaction mixture was heated at 155° C. for 6 hours until the reaction has ended. The mixture was then cooled down to 110°-115° C., and 60 g of water were gradually added, as the result of which the reaction complex gave off carbon dioxide. After the evolution of carbon dioxide had ceased, the pH of the mixture was adjusted to 7-7.5 and the excess of o-anisidine was distilled off virtually quantitatively under reduced pressure. The residue was crystallized by adding a little ethylene diglycol monomethyl ether and, after precipitation with water, filtered off, washed and dried. Yield: 1460 g of product mixture of the formula ##STR6## in which the isomer ratio of product 1 (X¹ =H/X² =CN):product 2 (X¹ =CN/X² =H) was 75:25.

EXAMPLE 2

Step 1

374 g of 2,6-dichloro-3-cyano-4-methylpyridine were added to 1000 ml of 70% by weight aqueous ethylamine solution at not more than 30° C. The mixture was stirred at from 15° to 30° C. for 3 hours, and then precipitated with ice, and the precipitate was filtered off, washed with water and dried. This gave a mixture of 2-chloro-3-cyano-4-methyl-6-ethylaminopyridine (about 290 g) and 2-ethylamino-3-cyano-4-methyl-6-chloropyridine (about 96 g), which had a melting point of from 90° to 110° C. This mixture was dissolved in 600 ml of hot toluene. Cooling brought down a grayish white product of formula ##STR7## It was isolated by filtering with suction. Yield: 220 g, melting point: 128° C.

Step 2

Step 2 was carried out analogously to Example 1. The aniline derivative used was unsubstituted aniline.

This produced 270 g of a product of formula ##STR8## melting point: 96° C.

EXAMPLE 3

Step 1

440 g of 2,6-dichloro-3-cyano-4-methylpyridine were suspended in a mixture of 1000 ml of toluene and 300 ml of water. 230 g of 3-methoxypropylamine were then added at from 36° to 48° C. with cooling over 1 hour and the mixture was subsequently stirred at from 45° to 55° C. for 2 hours. The 141 g of sodium carbonate were added over 20 min and the mixture was subsequently stirred at from 45° to 55° C. for 10 hours and at 75° C. for a further 3 hours. It was then acidified with concentrated hydrochloric acid to about pH 1.5 and the bottom, aqueous layer was then separated off. This was followed by cooling to room temperature, followed by removal of the precipitated 2-chloro-3-cyano-4-methyl-6-(3-methoxypropylamino)-pyridine by filtration and isolation thereof as per Example 2.

This gave 370 g of a isomerically pure (3-cyano) product having a melting point of 106° C.

Step 2

Step 2 was carried out analogously to Example 1. The aniline derivative used was o-anisidine.

This gave 507 g of a product of the formula ##STR9## melting point; 120° C.

The same method gives the compounds of the formula ##STR10## listed in the following table:

    __________________________________________________________________________     Ex. No.                                                                             L.sup.1                                                                           L.sup.2                                                                            L.sup.3                                                                            L.sup.4                                                                            L.sup.5    mp. [°C.]                                __________________________________________________________________________     4    H  H   H   H   C.sub.3 H.sub.6 OCH.sub.3                                                                 88                                              5    C.sub.3 H.sub.7                                                                   H   H   H   C.sub.3 H.sub.6 OCH.sub.3                                                                 75                                              6    CH.sub.3                                                                          H   H   H   C.sub.2 H.sub.4 OH                                                                        140                                             7    CH.sub.3                                                                          H   H   H   C.sub.4 H.sub.8 OH                                                                        68                                              8    CH.sub.3                                                                          H   H   H   CH(CH.sub.3)CH.sub.2 OH                                    9    CH.sub.3                                                                          H   H   H   C.sub.2 H.sub.5                                            10   CH.sub.3                                                                          H   H   H   C.sub.2 H.sub.4 OCH.sub.3                                                                 98                                              11   CH.sub.3                                                                          H   H   H   C.sub.3 H.sub.6 OC.sub.2 H.sub.5                           12   CH.sub.3                                                                          H   H   H   C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                        13   CH.sub.3                                                                          H   H   H   n-C.sub.3 H.sub.7                                                                         85                                              14   CH.sub.3                                                                          H   H   H   i-C.sub.3 H.sub.7                                                                         125                                             15   CH.sub.3                                                                          H   H   H   CH(CH.sub.3)C.sub.2 H.sub.5                                16   CH.sub.3                                                                          H   H   H   n-C.sub.4 H.sub.9                                                                         45                                              17   CH.sub.3                                                                          H   H   H   CH.sub.2 CHCH.sub.2                                        18   CH.sub.3                                                                          H   H   H   C.sub.2 H.sub.4 OC.sub.2 H.sub.5                           19   CH.sub.3                                                                          H   H   H   C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                        20   CH.sub.3                                                                          H   H   H   n-C.sub.5 H.sub.11                                         21   CH.sub.3                                                                          H   H   H                                                                                   ##STR11##                                                 22   CH.sub.3                                                                          H   H   H                                                                                   ##STR12##                                                 23   CH.sub.3                                                                          H   H   H   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                Resin                                           24   CH.sub.3                                                                          H   H   H   CH.sub.2 C.sub.6 H.sub.5                                   25   CH.sub.3                                                                          H   H   H   C.sub.2 H.sub.4 C.sub.6 H.sub.5                            26   CH.sub.3                                                                          H   H   H   CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5                       27   CH.sub.3                                                                          H   H   H                                                                                   ##STR13## 120                                             28   CH.sub.3                                                                          H   H   H   C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                       40                                              29   CH.sub.3                                                                          H   H   H   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5          30   H  H   H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OCH.sub.3                                                                 76                                              31   C.sub.3 H.sub.7                                                                   H   H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OCH.sub.3                                                                 55                                              32   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.2 H.sub.4 OH                                         33   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OH                                         34   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          CH(CH.sub.3)CH.sub.2 OH                                    35   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.2 H.sub.5                                            36   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.2 H.sub.4 OCH.sub.3                                  37   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                          80                                              38   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                        39   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                         80                                              40   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          i-C.sub.3 H.sub.7                                                                         150                                             41   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          CH(CH.sub.3)C.sub.2 H.sub.5                                42   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          n-C.sub.4 H.sub.9                                          43   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          CH.sub.2 CHCH.sub.2                                        44   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                          86                                              45   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                        46   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          n-C.sub.5 H.sub.11                                         47   CH.sub.3                                                                          H   H   OCH.sub.3                                                                           ##STR14##                                                 48   CH.sub.3                                                                          H   H   OCH.sub.3                                                                           ##STR15## 101                                             49   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                Resin                                           50   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          CH.sub.2 C.sub.6 H.sub.5                                   51   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.2 H.sub.4 C.sub.6 H.sub.5                            52   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5                       53   CH.sub.3                                                                          H   H   OCH.sub.3                                                                           ##STR16## 120                                             54   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OC.sub.2 H.sub.8 OH                        55   CH.sub.3                                                                          H   H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5          56   H  H   OCH.sub.3                                                                          H   C.sub.3 H.sub.6 OCH.sub.3                                  57   C.sub.3 H.sub.7                                                                   H   OCH.sub.3                                                                          H   C.sub.3 H.sub.6 OCH.sub.3                                  58   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.2 H.sub.4 OH                                         59   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.3 H.sub.6 OH                                         60   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   CH(CH.sub.3)CH.sub.2 OH                                    61   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.2 H.sub.5                                            62   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.2 H.sub.4 OCH.sub.3                                  63   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.3 H.sub.6 OC.sub.2 H.sub.5                           64   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                        65   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   n-C.sub.3 H.sub.7                                          66   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   i-C.sub.3 H.sub.7                                                                         135                                             67   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   CH(CH.sub.3)C.sub.2 H.sub.5                                68   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   n-C.sub.4 H.sub.9                                          69   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   CH.sub.2 CHCH.sub.2                                        70   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.2 H.sub.4 OC.sub.2 H.sub.5                           71   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                        72   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   n-C.sub.5 H.sub.11                                         73   CH.sub.3                                                                          H   OCH.sub.3                                                                          H                                                                                   ##STR17##                                                 74   CH.sub.3                                                                          H   OCH.sub.3                                                                          H                                                                                   ##STR18##                                                 75   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                Resin                                           76   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   CH.sub.2 C.sub.6 H.sub.5                                   77   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.2 H.sub.4 C.sub.6 H.sub.5                            78   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5                       79   CH.sub.3                                                                          H   OCH.sub.3                                                                          H                                                                                   ##STR19##                                                 80   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                        81   CH.sub.3                                                                          H   OCH.sub.3                                                                          H   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5          82   H  OCH.sub.3                                                                          H   H   C.sub.3 H.sub.6 OCH.sub.3                                  83   C.sub.3 H.sub.7                                                                   OCH.sub.3                                                                          H   H   C.sub.3 H.sub.6 OCH.sub.3                                  84   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.2 H.sub.4 OH                                         85   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.3 H.sub.6 OH                                         86   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   CH(CH.sub.3)CH.sub.2 OH                                    87   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.2 H.sub.5                                            88   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.2 H.sub.4 OCH.sub.3                                  89   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.3 H.sub.6 OC.sub.2 H.sub.5                           90   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                                                       Resin                                           91   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   n-C.sub.3 H.sub.7                                          92   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   i-C.sub.3 H.sub.7                                          93   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   CH(CH.sub.3)C.sub.2 H.sub.5                                94   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   n-C.sub.4 H.sub.9                                          95   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   CH.sub.2 CHCH.sub.2                                        96   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.2 H.sub.4 OC.sub.2 H.sub.5                           97   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.2 H.sub.4L OC.sub.2 H.sub.4 OH                       98   CH.sub.3                                                                          OCH.sub.3                                                                          H   H   n-C.sub.5 H.sub.11                                         99   CH.sub.3                                                                          OCH.sub.3                                                                          H   H                                                                                   ##STR20##                                                 100  CH.sub.3                                                                          OCH.sub.3                                                                          H   H                                                                                   ##STR21##                                                 101  CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                 102  CH.sub.3                                                                          OCH.sub.3                                                                          H   H   CH.sub.2 C.sub.6 H.sub.5                                   103  CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.2 H.sub.4L C.sub.6 H.sub.5                           104  CH.sub.3                                                                          OCH.sub.3                                                                          H   H   CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5                       105  CH.sub.3                                                                          O   H   CH.sub.3                                                                            ##STR22##                                                 106  CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                        107  CH.sub.3                                                                          OCH.sub.3                                                                          H   H   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5          108  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OCH.sub.3                                                                 86                                              109  C.sub.3 H.sub.7                                                                   CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OCH.sub.3                                  110  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.2 H.sub.4 OH                                         111  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OH                                         112  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          CH(CH.sub.3)CH.sub.2 OH                                    113  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.2 H.sub.5                                            114  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.2 H.sub. 4 OCH.sub.3                                 115  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OC.sub.2 H.sub.5                                                          75                                              116  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                                                       Resin                                           117  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          n-C.sub.3 H.sub.7                                                                         147                                             118  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          i-C.sub.3 H.sub.7                                                                         150                                             119  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          CH(CH.sub.3)C.sub.2 H.sub.5                                120  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          n-C.sub.4 H.sub.9                                          121  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          CH.sub.2 CHCH.sub.2                                        122  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.2 H.sub.4 OC.sub.2 H.sub.5                                                          95                                              123  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                        124  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          n-C.sub.5 H.sub.11                                         125  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR23##                                                 126  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR24##                                                 127  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                 128  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          CH.sub.2 C.sub.6 H.sub.5                                   129  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.2 H.sub.4 C.sub.6 H.sub.5                            130  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5                       131  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                           ##STR25## 116                                             132  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                        133  CH.sub.3                                                                          CH.sub.3                                                                           H   OCH.sub.3                                                                          C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5          134  H  H   H   CH.sub.3                                                                           C.sub.3 H.sub.6 OCH.sub.3                                  135  C.sub.3 H.sub.7                                                                   H   H   CH.sub.3                                                                           C.sub.3 H.sub.6 OCH.sub.3                                  136  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.2 H.sub.4 OH                                         137  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.3 H.sub.6 OH                                         138  CH.sub.3                                                                          H   H   CH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 OH                                    139  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.2 H.sub.5                                            140  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.2 H.sub.4 OCH.sub.3                                  141  CH.sub. 3                                                                         H   H   CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.2 H.sub.5                           142  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                                                       Resin                                           143  CH.sub.3                                                                          H   H   CH.sub.3                                                                           n-C.sub.3 H.sub.7                                                                         92                                              144  CH.sub.3                                                                          H   H   CH.sub.3                                                                           i-C.sub.3 H.sub.7                                          145  CH.sub.3                                                                          H   H   CH.sub.3                                                                           CH(CH.sub.3)C.sub.2 H.sub.5                                146  CH.sub.3                                                                          H   H   CH.sub.3                                                                           n-C.sub.4 H.sub.9                                          147  CH.sub.3                                                                          H   H   CH.sub.3                                                                           CH.sub.2 CHCH.sub.2                                        148  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.2 H.sub.4 OC.sub.2 H.sub.5                           149  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                        150  CH.sub.3                                                                          H   H   CH.sub.3                                                                           n-C.sub.5 H.sub.11                                         151  CH.sub.3                                                                          H   H   CH.sub.3                                                                            ##STR26##                                                 152  CH.sub.3                                                                          H   H   CH.sub.3                                                                            ##STR27##                                                 153  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                Resin                                           154  CH.sub.3                                                                          H   H   CH.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.5                                   155  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.2 H.sub.4 C.sub.6 H.sub.5                            156  CH.sub.3                                                                          H   H   CH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5                       157  CH.sub.3                                                                          H   H   CH.sub.3                                                                            ##STR28## 112                                             158  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                        159  CH.sub.3                                                                          H   H   CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5          160  H  H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.3 H.sub.6 OCH.sub.3                                  161  C.sub.3 H.sub.7                                                                   H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.3 H.sub.6 OCH.sub.3                                  162  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.4 OH                                         163  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.3 H.sub.6 OH                                         164  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 OH                                    165  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.5                                            166  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.4 OCH.sub.3                                  167  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.2 H.sub.5                           168  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                                                       Resin                                           169  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           n-C.sub.3 H.sub.7                                          170  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           i-C.sub.3 H.sub.7                                          171  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           CH(CH.sub.3)C.sub.2 H.sub.5                                172  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           n-C.sub.4 H.sub.9                                          173  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 CHCH.sub.2                                        174  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.4 OC.sub.2 H.sub.5                           175  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                        176  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           n-C.sub.5 H.sub.11                                         177  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                            ##STR29##                                                 178  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                            ##STR30##                                                 179  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                Resin                                           180  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.5                                   181  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.2 H.sub.4 C.sub.6 H.sub.5                            182  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5                       183  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                            ##STR31## 110                                             184  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                        185  CH.sub.3                                                                          H   CH.sub.3                                                                           CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5          186  H  CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.3 H.sub.6 OCH.sub.3                                  187  C.sub.3 H.sub.7                                                                   CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.3 H.sub.6 OCH.sub.3                                  188  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.2 H.sub.4 OH                                         189  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.3 H.sub.6 OH                                         190  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 OH                                    191  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.2 H.sub.5                                            192  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.2 H.sub.4 OCH.sub.3                                  193  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.2 H.sub.5                           194  CH.sub.3                                                                          CH.sub. 3                                                                          H   CH.sub.3                                                                           C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                        195  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           n-C.sub.3 H.sub.7                                          196  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           i-C.sub.3 H.sub.7                                          197  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           CH(CH.sub.3)C.sub.2 H.sub.5                                198  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           n-C.sub.4 H.sub.9                                          199  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           CH.sub.2 CHCH.sub.2                                        200  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.2 H.sub.4 OC.sub.2 H.sub.5                           201  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                        202  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           n-C.sub.5 H.sub.11                                         203  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                            ##STR32##                                                 204  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                            ##STR33##                                                 205  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                                                Resin                                           206  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           CH.sub.2 C.sub.6 H.sub.5                                   207  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.2 H.sub.4 C.sub.6 H.sub.5                            208  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5                       209  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                            ##STR34##                                                 210  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                       35                                              211  CH.sub.3                                                                          CH.sub.3                                                                           H   CH.sub.3                                                                           C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5          212  H  H   C.sub.2 H.sub.5                                                                    H   C.sub.3 H.sub.6 OCH.sub.3                                  213  C.sub.3 H.sub.7                                                                   H   C.sub.2 H.sub.5                                                                    H   C.sub.3 H.sub.6 OCH.sub.3                                  214  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.2 H.sub.4 OH                                         215  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.3 H.sub.6 OH                                         216  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   CH(CH.sub.3)CH.sub.2 OH                                    217  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.2 H.sub.5                                            218  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.2 H.sub.4 OCH.sub.3                                  219  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.3 H.sub.6 OC.sub.2 H.sub.5                           220  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                                                       Resin                                           221  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   n-C.sub.3 H.sub.7                                          222  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   i-C.sub.3 H.sub.7                                          223  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   CH(CH.sub.3)C.sub.2 H.sub.5                                224  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   n-C.sub.4 H.sub.9                                          225  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   CH.sub.2 CHCH.sub.2                                        226  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.2 H.sub.4 OC.sub.2 H.sub.5                           227  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                        228  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   n-C.sub.5 H.sub.11                                         229  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H                                                                                   ##STR35##                                                 230  CH.sub.3                                                                          H   CH.sub.3                                                                           H                                                                                   ##STR36## 130                                             231  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.3 H.sub.6 OC.sub.2 H.sub.4L OCH.sub.3                232  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   CH.sub.2 C.sub.6 H.sub.5                                   233  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.2 H.sub.4 C.sub.6 H.sub.5                            234  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5                       235  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H                                                                                   ##STR37## 108                                             236  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                                                       36                                              237  CH.sub.3                                                                          H   C.sub.2 H.sub.5                                                                    H   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5          238  H  CH.sub.3                                                                           H   H   C.sub.3 H.sub.6 OCH.sub.3                                  239  C.sub.3 H.sub.7                                                                   CH.sub.3                                                                           H   H   C.sub.3 H.sub.6 OCH.sub.3                                  240  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.2 H.sub.4 OH                                         241  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.3 H.sub.6 OH                                         242  CH.sub.3                                                                          CH.sub.3                                                                           H   H   CH(CH.sub.3)CH.sub.2 OH                                    243  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.2 H.sub.5                                            244  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.2 H.sub.4 OCH.sub.3                                  245  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.3 H.sub.6 OC.sub.2 H.sub.5                           246  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.3 H.sub.6 OCH(CH.sub.3).sub.2                                                       Resin                                           247  CH.sub.3                                                                          CH.sub.3                                                                           H   H   n-C.sub.3 H.sub.7                                          248  CH.sub.3                                                                          CH.sub.3                                                                           H   H   i-C.sub.3 H.sub.7                                                                         105                                             249  CH.sub.3                                                                          CH.sub.3                                                                           H   H   CH(CH.sub.3)C.sub.2 H.sub.5                                250  CH.sub.3                                                                          CH.sub.3                                                                           H   H   n-C.sub.4 H.sub.9                                          251  CH.sub.3                                                                          CH.sub.3                                                                           H   H   CH.sub.2 CHCH.sub.2                                        252  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.2 H.sub.4 OC.sub.2 H.sub.5                           253  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.2 H.sub.4 OC.sub.2 H.sub.4 OH                        254  CH.sub.3                                                                          CH.sub.3                                                                           H   H   n-C.sub.5 H.sub.11                                         255  CH.sub.3                                                                          CH.sub.3                                                                           H   H                                                                                   ##STR38##                                                 256  CH.sub.3                                                                          CH.sub.3                                                                           H   H                                                                                   ##STR39## 110                                             257  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OCH.sub.3                 258  CH.sub.3                                                                          CH.sub.3                                                                           H   H   CH.sub.2 C.sub.6 H.sub.5                                   259  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub. 2 H.sub.4 C.sub.6 H.sub.5                           260  CH.sub.3                                                                          CH.sub.3                                                                           H   H   CH(CH.sub.3)CH.sub.2 C.sub.6 H.sub.5                       261  CH.sub.3                                                                          CH.sub.3                                                                           H   H                                                                                   ##STR40## 127                                             262  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                        263  CH.sub.3                                                                          CH.sub.3                                                                           H   H   C.sub.3 H.sub.6 OC.sub.2 H.sub.4 OC.sub.6 H.sub.5          264  CH.sub.3                                                                          H   H   H   C.sub.3 H.sub.6 OC.sub.4 H.sub.8 OH                        265  CH.sub.3                                                                          H   n-C.sub.4 H.sub.9                                                                  H   i-C.sub.3 H.sub.7                                                                         92                                                                             (hydrochloride)                                 266  CH.sub.3                                                                          H   H   OCH.sub.3                                                                          CH(C.sub.2 H.sub.5)CH.sub.2 OCH.sub.3                                                     46                                              267  CH.sub.3                                                                          H   H   OCH.sub.3                                                                           ##STR41## 105                                             268  CH.sub.3                                                                          H   H   h   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            120                                                                            (pure isomer)                                   269  CH.sub.3                                                                          H   H   H   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            114                                                                            (mixed isomers)                                 270  CH.sub.3                                                                          H   OCH.sub.3                                                                          H   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            90                                              271  CH.sub.3                                                                          H   CH.sub.3                                                                           H   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            110                                             272  CH.sub.3                                                                          H   H   H   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            114                                             273  CH.sub.3                                                                          H   H   H   CH(CH.sub.3)CH.sub.2 OCH.sub.3                                                            80                                              __________________________________________________________________________ 

We claim:
 1. A process for preparing diaminopyridines of the formula I ##STR42## where one of the two radicals X¹ and X² is hydrogen, C₁ -C₄ -alkyl, halogen or nitro and the other is cyano,R¹ is hydrogen, C₁ -C₄ -alkyl or phenyl, R² and R³ are each independently of one another hydrogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, R⁴ is hydrogen or C₁ -C₄ -alkyl, and R⁵ is C₁ -C₁₀ -alkyl which may be interrupted by from 1 to 3 oxygen atoms in ether function and is optionally hydroxyl-, C₁ -C₄ -alkanoyloxy-, phenoxy-, phenyl-, tetrahydrofuranyl- or tetrahydropyranyl-substituted, C₃ -C₄ -alkenyl or C₅ -C₇ -cycloalkyl,by reacting dichloropyridines of the formula II ##STR43## where R¹ and X¹ are each as defined above, with amines by reacting in a first step a dichloropyridine of the formula II with an amine of the formula III

    R.sup.5 --NH.sub.2                                         (III)

where R⁵ is as defined above, at from 10° to 80° C. in the presence of a base and of an inert organic diluent and/or water, then removing the diluent and thereafter, with or without prior intermediate isolation of the reaction product, reacting it in a second step with an aniline of the formula IV ##STR44## where R², R³ and R⁴ are each as defined above, which comprises carrying out the second step in a melt at from 90° to 165° C. and at a pH from 3.5 to 6.5 using from 1.3 to 3 mol of aniline IV are used per mole of dichloropyridine II.
 2. A process as claimed in claim 1, wherein in the formula I, X¹ is hydrogen and X² is cyano.
 3. A process as claimed in claim 1, wherein in the formula I, R¹ is methyl.
 4. A process as claimed in claim 1, wherein the diluent used in the first step is isobutanol, toluene, o-, m- or p-xylene, ethylbenzene or a mixture thereof. 